{"id":{"repo_id":"cork","oai_identifier":"oai:cora.ucc.ie:10468/15075"},"canonical_url":"https://search.dev.ndltd.org/etd/cork/oai:cora.ucc.ie:10468/15075","repository":{"repo_id":"cork","name":"University College Cork","base_url":"https://cora.ucc.ie/server/oai/request"},"display":{"title":"Synthesis of novel cycloperoxides","abstract":"Cycloperoxides represent an important class of compounds for synthetic chemists. Their asymmetric synthesis will be the focus of this thesis, specifically using organocatalysis. Chapter 1 contains a review of organocatalysed peroxidations from the literature and within the research group to date. The key aims and objectives of this project are also outlined. Chapter 2 describes the generation of a diverse library of trans-γ,δ-unsaturated β-keto esters. The preparation of these compounds involves both Wittig chemistry and Lewis acid-catalysed C-H insertion strategies. The synthesis of a cis-γ,δ-unsaturated β-keto ester and a non-enolisable α,α-disubstituted β-keto ester are also outlined. The optimisation of the organocatalysed peroxidation of γ,δ-unsaturated β-keto esters in terms of enantioselectivity and yields is described in Chapter 3. To determine the enantioselectivity of the peroxidation reaction, a robust chiral HPLC methodology is required. The development of a suitable separation methodology is outlined in this chapter. Chapter 4 describes a novel synthetic route to 3,5-substituted 1,2-dioxolane ethyl esters through the chemoselective reduction of a δ-peroxy-β-keto ester to the corresponding δ-peroxy-β-hydroxy ester, and subsequent phosphorus pentoxide-mediated cyclisation. Chapter 5 outlines our preparation of several novel 1,2-dioxolane carboxylic acids and various attempts at subsequently introducing an N-acyl sulfonamide to the 1,2-dioxolane core. Chapter 6 details the main conclusions of this work and proposes several avenues of research to investigate in future. Chapter 7 contains all relevant experimental procedures, including spectroscopic and analytical data.","abstract_html":"Cycloperoxides represent an important class of compounds for synthetic chemists. Their asymmetric synthesis will be the focus of this thesis, specifically using organocatalysis. Chapter 1 contains a review of organocatalysed peroxidations from the literature and within the research group to date. The key aims and objectives of this project are also outlined. Chapter 2 describes the generation of a diverse library of trans-γ,δ-unsaturated β-keto esters. The preparation of these compounds involves both Wittig chemistry and Lewis acid-catalysed C-H insertion strategies. The synthesis of a cis-γ,δ-unsaturated β-keto ester and a non-enolisable α,α-disubstituted β-keto ester are also outlined. The optimisation of the organocatalysed peroxidation of γ,δ-unsaturated β-keto esters in terms of enantioselectivity and yields is described in Chapter 3. To determine the enantioselectivity of the peroxidation reaction, a robust chiral HPLC methodology is required. The development of a suitable separation methodology is outlined in this chapter. Chapter 4 describes a novel synthetic route to 3,5-substituted 1,2-dioxolane ethyl esters through the chemoselective reduction of a δ-peroxy-β-keto ester to the corresponding δ-peroxy-β-hydroxy ester, and subsequent phosphorus pentoxide-mediated cyclisation. Chapter 5 outlines our preparation of several novel 1,2-dioxolane carboxylic acids and various attempts at subsequently introducing an N-acyl sulfonamide to the 1,2-dioxolane core. Chapter 6 details the main conclusions of this work and proposes several avenues of research to investigate in future. Chapter 7 contains all relevant experimental procedures, including spectroscopic and analytical data.","abstract_has_math":false,"creators":["Hennessy, Mary C."],"institution":"University College Cork","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["O'Sullivan, Tim"],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023","date_published":"2023","updated_at":"2026-07-24T01:48:18Z","subjects":["Cycloperoxides","Peroxidation","1,2-Dioxolane","Cyclisation","γ,δ-unsaturated β-keto esters","Asymmetric synthesis","Organocatalysis"],"languages":["en"],"rights":["© 2023, Mary Constance Hennessy."],"rights_urls":["https://creativecommons.org/licenses/by-nc-nd/4.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/10468/15075","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["O'Sullivan, Tim"]},{"key":"dc:creator","label":"Author","values":["Hennessy, Mary C."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2023-10-06T10:30:52Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2023-10-06T10:30:52Z"]},{"key":"dc:date.issued","label":"Date","values":["2023"]},{"key":"dc:publisher","label":"Institution","values":["University College Cork"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD - Doctor of Philosophy"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Cycloperoxides","Peroxidation","1,2-Dioxolane","Cyclisation","γ,δ-unsaturated β-keto esters","Asymmetric synthesis","Organocatalysis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["© 2023, Mary Constance Hennessy."]},{"key":"dc:rights.uri","label":"Rights URI","values":["https://creativecommons.org/licenses/by-nc-nd/4.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10468/15075"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Controlled Access"]},{"key":"dc:description.abstract","label":"Abstract","values":["Cycloperoxides represent an important class of compounds for synthetic chemists. Their asymmetric synthesis will be the focus of this thesis, specifically using organocatalysis. Chapter 1 contains a review of organocatalysed peroxidations from the literature and within the research group to date. The key aims and objectives of this project are also outlined. Chapter 2 describes the generation of a diverse library of trans-γ,δ-unsaturated β-keto esters. The preparation of these compounds involves both Wittig chemistry and Lewis acid-catalysed C-H insertion strategies. The synthesis of a cis-γ,δ-unsaturated β-keto ester and a non-enolisable α,α-disubstituted β-keto ester are also outlined. The optimisation of the organocatalysed peroxidation of γ,δ-unsaturated β-keto esters in terms of enantioselectivity and yields is described in Chapter 3. To determine the enantioselectivity of the peroxidation reaction, a robust chiral HPLC methodology is required. The development of a suitable separation methodology is outlined in this chapter. Chapter 4 describes a novel synthetic route to 3,5-substituted 1,2-dioxolane ethyl esters through the chemoselective reduction of a δ-peroxy-β-keto ester to the corresponding δ-peroxy-β-hydroxy ester, and subsequent phosphorus pentoxide-mediated cyclisation. Chapter 5 outlines our preparation of several novel 1,2-dioxolane carboxylic acids and various attempts at subsequently introducing an N-acyl sulfonamide to the 1,2-dioxolane core. Chapter 6 details the main conclusions of this work and proposes several avenues of research to investigate in future. Chapter 7 contains all relevant experimental procedures, including spectroscopic and analytical data."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis of novel cycloperoxides"]}]}],"canonical_facts":{"dc:contributor.advisor":["O'Sullivan, Tim"],"dc:creator":["Hennessy, Mary C."],"dc:date.accessioned":["2023-10-06T10:30:52Z"],"dc:date.available":["2023-10-06T10:30:52Z"],"dc:date.issued":["2023"],"dc:description":["Controlled Access"],"dc:description.abstract":["Cycloperoxides represent an important class of compounds for synthetic chemists. Their asymmetric synthesis will be the focus of this thesis, specifically using organocatalysis. Chapter 1 contains a review of organocatalysed peroxidations from the literature and within the research group to date. The key aims and objectives of this project are also outlined. Chapter 2 describes the generation of a diverse library of trans-γ,δ-unsaturated β-keto esters. The preparation of these compounds involves both Wittig chemistry and Lewis acid-catalysed C-H insertion strategies. The synthesis of a cis-γ,δ-unsaturated β-keto ester and a non-enolisable α,α-disubstituted β-keto ester are also outlined. The optimisation of the organocatalysed peroxidation of γ,δ-unsaturated β-keto esters in terms of enantioselectivity and yields is described in Chapter 3. To determine the enantioselectivity of the peroxidation reaction, a robust chiral HPLC methodology is required. The development of a suitable separation methodology is outlined in this chapter. Chapter 4 describes a novel synthetic route to 3,5-substituted 1,2-dioxolane ethyl esters through the chemoselective reduction of a δ-peroxy-β-keto ester to the corresponding δ-peroxy-β-hydroxy ester, and subsequent phosphorus pentoxide-mediated cyclisation. Chapter 5 outlines our preparation of several novel 1,2-dioxolane carboxylic acids and various attempts at subsequently introducing an N-acyl sulfonamide to the 1,2-dioxolane core. Chapter 6 details the main conclusions of this work and proposes several avenues of research to investigate in future. Chapter 7 contains all relevant experimental procedures, including spectroscopic and analytical data."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://hdl.handle.net/10468/15075"],"dc:language.iso":["en"],"dc:publisher":["University College Cork"],"dc:rights":["© 2023, Mary Constance Hennessy."],"dc:rights.uri":["https://creativecommons.org/licenses/by-nc-nd/4.0/"],"dc:subject":["Cycloperoxides","Peroxidation","1,2-Dioxolane","Cyclisation","γ,δ-unsaturated β-keto esters","Asymmetric synthesis","Organocatalysis"],"dc:title":["Synthesis of novel cycloperoxides"],"dc:type":["Doctoral thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD - Doctor of Philosophy"]},"updated_at":"2026-07-24T01:48:18Z"}